TWI710659B - Siloxane compositions and methods for using the compositions to deposit silicon containing films - Google Patents

Abstract

The siloxanes containing compositions and methods are disclosed. The disclosed method relates to a method of depositing a dielectric film on a substrate, the method involving the steps of a) placing the substrate in a reaction chamber; b) introducing a process gas comprising a cyclic silicon-containing compound and an oxidant; and c) exposing the substrate to the process gas under conditions such that the cyclic silicon-containing compound and the oxidant react to form a flowable film on the substrate surface. The method can further involve converting the flowable film into a solid dielectric material (e.g., a silicon oxide film). In certain embodiments, conversion of the film may be accomplished by annealing the as-deposited film by a thermal, plasma anneal and/UV curing.

Description

Silicone composition and method for depositing silicon-containing film using the composition

Cross reference of applications This case requests the priority of the previous U.S. Patent Application Serial No. 62/685,867 filed on June 15, 2018 under the protection of 35 USC § 119(e), and the full content of its disclosure is incorporated herein by reference. Into this article.

The invention relates to a cyclic silane composition and a method for depositing a silicon-containing film using the cyclic silane composition.

It is known in this art to use a flowable chemical vapor deposition process to deposit silicon oxide films by vapor phase polymerization. For example, prior art has focused on using compounds such as trisilylamine (TSA) to deposit Si, H, and N-containing oligomers, which are then oxidized into SiOx films using ozone exposure. This example is disclosed in: U.S. Publication No. 2014/0073144; U.S. Publication No. 2013/230987; U.S. Patent No. 7,521,378, U.S. Patent Nos. 7,557,420 and 8,575,040; and U.S. Patent No. 7,825,040. These processes always require high-temperature steam treatment and thermal annealing at> 1000 ^o C.

US Patent No. 7,825,038 B2 discloses a method of depositing a silicon oxide layer on a substrate, which includes the following steps: providing the substrate in a deposition chamber, generating an atomic oxygen precursor outside the deposition chamber, and the atomic oxygen precursor Introduce the cabin. The deposition may also include introducing a silicon precursor into the deposition chamber, where the silicon precursor and the atomic oxygen precursor are first mixed in the chamber. Precursors such as octamethyltrisiloxane (OMTS), octamethylcyclotetrasiloxane (OMCTS) and tetramethylcyclotetrasiloxane (TOMCATS) are used for this application.

U.S. Patent Nos. 7998536, 7989033 and Yim, KS (2009) "Novel silicon precursors to make ultra low-k films with high mechanical properties by plasma enhanced chemical vapor deposition" disclose the use of low-k, Si-C containing Film precursors and methods.

US Patent No. 9362107 B2 discloses a method of forming a flowable low-k dielectric film on a patterned substrate. The film may be a silicon-carbon-oxygen (Si-CO) layer, where the silicon and carbon constituents come from precursors containing silicon and carbon, and the oxygen may come from oxygen-containing precursors activated in the remote plasma region . Soon after deposition, before curing, the silicon-carbon-oxygen layer is treated by exposure to hydrogen and nitrogen-containing precursors such as ammonia. This treatment can remove residual moisture from the silicon-carbon-oxygen layer and can make the crystal lattice more elastic during curing and subsequent processing. This treatment can reduce the shrinkage of the silicon-carbon-oxygen layer during subsequent processing. The case claims to protect precursors such as octamethylcyclotetrasiloxane (OMCTS) and tetramethylcyclotetrasiloxane (TOMCATS).

This known precursor and deposition process can deposit a hydrophilic film that absorbs moisture and leads to an increase in dielectric constant.

The disclosures of previously identified patents and patent applications are incorporated herein by reference.

The present invention solves the problems associated with known precursors and processes by providing a cyclic silane composition and a method for depositing a silicon-containing film and a film that fills the gaps between various features of a semiconductor in a specific example.

式I 其中R^1-4 係獨立地選自氫、直鏈或分支C₁ 至C₁₀ 烷基、直鏈或分支C₃ 至C₁₀ 烯基、直鏈或分支C₃ 至C₁₀ 炔基、二-C₁ 至C₆ -烷基胺基及C₆ 至C₁₀ 芳基，而且n= 1、2、3、4。控制該反應器條件，使該含矽化合物及該活化物種反應並且於該基材上縮合為可流動膜。該至少一活化物種係相對於該反應艙以遠距活化。More particularly, the present invention includes a flowable chemical vapor deposition method for forming a silicon-containing film on a substrate. The method includes putting the substrate into a reaction chamber and introducing at least one cyclic siloxane compound represented by formula I and at least one activated species into the chamber,

Formula I wherein R ^1-4 are independently selected from hydrogen, linear or branched C ₁ to C ₁₀ alkyl, linear or branched C ₃ to C ₁₀ alkenyl, linear or branched C ₃ to C ₁₀ alkynyl, Di-C ₁ to C ₆ -alkylamino and C ₆ to C ₁₀ aryl, and n = 1, 2, 3, 4. The conditions of the reactor are controlled to allow the silicon-containing compound and the activated species to react and condense on the substrate into a flowable film. The at least one activated species is activated remotely from the reaction chamber.

The flowable film has at least one of Si-C and Si-O bonds in some cases. The flowable film fills the high aspect ratio gaps on the surface features of the substrate. The flowable film is then converted into the final silicon oxide film, for example, by plasma, UV and/or thermal annealing. The method of the present invention can be used to fill gaps with high aspect ratios, including gaps with an aspect ratio ranging from 3:1 to 10:1 or greater.

The activated species can be produced using a remote plasma source, a remote microwave source, or a remote hot-wire system.

According to a specific example, the at least one activated species acts on a plasma source or a remote microwave source selected from water vapor, ozone, oxygen, oxygen/helium, oxygen/argon, nitrogen oxide, carbon dioxide, hydrogen peroxide, An oxidant produced by species in the group consisting of organic peroxides and their mixtures.

According to another specific example, the at least one activated species acts on a plasma source or a remote microwave source selected from the group consisting of nitrogen, a mixture of nitrogen and helium, a mixture of nitrogen and argon, ammonia, a mixture of ammonia and helium, ammonia and Species produced in the group consisting of argon mixtures, helium, argon, hydrogen, hydrogen and helium mixtures, hydrogen and argon mixtures, ammonia and hydrogen mixtures, organic amines and their mixtures.

According to another specific example, the at least one cyclic siloxane compound comprises 2,2,5,5-tetramethyl-1-oxa-2,5-disilolane and 2,2,6, One or both of 6-tetramethyl-1-oxa-2,6-disilane.

After performing the above steps, the flowable film can be processed by a processing method selected from the group consisting of plasma, UV radiation and thermal annealing. Treating the flowable film with this processing method converts the flowable film into a dielectric material.

As mentioned above, some specific examples of the present invention involve the use of the above-mentioned method of forming a dielectric film to achieve the purpose of filling the gaps on the substrate with the dielectric. In this specific example, the silicon-containing compound and the oxidizing agent react in the gap to form a flowable film before converting the flowable film into a dielectric material.

In yet another specific example, the silicon-containing film is deposited in the gap via a plasma assisted reaction. In this specific example, after the plasma assisted reaction and the silicon-containing film is deposited in the gap, an oxidant is introduced into the reaction chamber, and the silicon-containing film is exposed to the oxidant so as to include Si-O and Si-C bonds At least one of the flowable films is formed in the gap. The original deposited film is then converted into a dielectric material.

Another aspect of the invention relates to the film obtained by the method of the invention.

Another specific example relates to a composition for depositing a flowable chemical vapor film on a substrate. The composition includes 2,2,5,5-tetramethyl-1-oxa-2,5 -Disilolane with less than 10 ppm halide impurity, the halide is selected from the group consisting of chloride, fluoride, bromide and iodide.

Another specific example relates to a composition for depositing a flowable chemical vapor film on a substrate. The composition includes 2,2,5,5-tetramethyl-1-oxa-2,5 -Disilolane and has a metal ion impurity of less than 10 ppm. The metal ion is selected from the group consisting of Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ and Cr ³⁺ .

Another specific example relates to a composition for depositing a flowable chemical vapor film on a substrate. The composition includes 2,2,6,6-tetramethyl-1-oxa-2,6 -Disilica and has less than 10 ppm halide impurity, the halide is selected from the group consisting of chloride, fluoride, bromide and iodide.

Another specific example relates to a composition for depositing a flowable chemical vapor film on a substrate. The composition includes 2,2,6,6-tetramethyl-1-oxa-2,6 -Disilane and has less than 10 ppm of metal ion impurities, and the metal ion is selected from the group consisting of Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ and Cr ³⁺ .

The various aspects of the present invention can be used alone or in combination with each other.

The detailed description that follows only provides preferred exemplary specific examples, and is not intended to limit the scope, applicability, or configuration of the present invention. More specifically, the following detailed descriptions of preferred exemplary specific examples are provided to those skilled in the art for the authorized description of preferred exemplary specific examples of the present invention. Different changes can be made in the function and arrangement of the components without departing from the spirit and scope of the invention as described in the appended patent scope.

In the scope of the patent application, letters can be used to identify the method steps (for example, a, b, and c) that have a claim. Unless and as long as this order is clearly listed in the scope of the application, these letters are used to assist in quoting the method steps and are not intended to indicate the order in which the claimed steps are carried out.

Flowable dielectric coatings can be achieved by using processes similar to those known in the art, such as those described in U.S. Patent Nos. 7,888,233, 7,582,555, and 7,915,139 B1; hereby incorporated by reference All the foregoing is incorporated into this article. Place the substrate to be coated into the deposition chamber. The temperature of the substrate can be controlled to be lower than the bulkhead. The temperature of the substrate is kept below 150°C, preferably below 80°C, most preferably below 60°C, and above -30°C. The preferred exemplary substrate temperature of the present invention is between -30° to 0°C, 0° to 20°C, 10° to 30°C, 20° to 40°C, 30° to 60°C, 40° to 80°C, 70° ° to 150 °C. The substrate may have small-sized features as needed, with a width of less than 100 μm, preferably a width of less than 1 μm, and most preferably a width of less than 0.5 μm. The aspect ratio (depth to width ratio) of the feature, if any, is greater than 0.1:1, preferably greater than 1:1, and most preferably greater than 2:1.

The substrate can be single crystal silicon wafer, silicon carbide wafer, alumina (sapphire) wafer, glass plate, metal foil layer, organic polymer film, or it can be polymerized, glass, silicon or metallic 3- Dimensional objects. The substrate can include silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, gallium arsenide, and gallium nitride films, including various materials that are well known in the art. Coating. These coatings can completely coat the substrate, possibly with multiple layers of different materials, and can be partially etched to expose the underlying material layer. There may also be a photoresist material on the surface, which is exposed and developed with a pattern to partially coat the substrate.

式I 其中R^1-4 係獨立地選自氫、直鏈或分支C₁ 至C₁₀ 烷基、直鏈或分支C₃ 至C₁₀ 烯基、直鏈或分支C₃ 至C₁₀ 炔基、C₁ 至C₆ 二烷基胺基及C₆ 至C₁₀ 芳基；n= 1、2、3、4。較佳為R^1-4 係獨立地選自氫及甲基。示範的具有式I的化合物包括，但不限於，2,2,5,5-四甲基-1-氧雜-2,5-二矽雜環戊烷、2,2,6,6-四甲基-1-氧雜-2,6-二矽雜環己烷。Although any suitable cyclic siloxane precursor can be used in accordance with the present invention, examples of suitable silicon precursors include at least one compound having the following structure:

Formula I wherein R ^1-4 are independently selected from hydrogen, linear or branched C ₁ to C ₁₀ alkyl, linear or branched C ₃ to C ₁₀ alkenyl, linear or branched C ₃ to C ₁₀ alkynyl, C ₁ to C ₆ dialkylamino group and C ₆ to C ₁₀ aryl group; n=1, 2, 3, 4. Preferably, R ^1-4 are independently selected from hydrogen and methyl. Exemplary compounds of formula I include, but are not limited to, 2,2,5,5-tetramethyl-1-oxa-2,5-disilolane, 2,2,6,6-tetra Methyl-1-oxa-2,6-disilane.

The silicon precursor compounds described herein can be delivered to the reaction chamber in various ways, such as a plasma enhanced CVD reactor. In a specific example, a liquid delivery system can be used. In an alternative specific example, a combined liquid transport and flash evaporation process unit may be used, such as, for example, a turbo vaporizer manufactured by MSP Co., Ltd. of Shoreway, Minnesota, to make Low-volatility materials can be transported by volume, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In the liquid delivery formulation, the precursors described herein can be delivered in pure liquid form, or can be used in a solvent formulation or a combination thereof. Therefore, in some specific examples, the precursor formulation may include suitable properties and solvent components that are advantageous in specific end-use applications to form a film on a substrate.

The deposition can be performed using direct plasma or remote plasma sources. For the remote plasma source, a dual plenum showerhead can be used to prevent the pre-mixing between the vapor of the silicon precursor and the free radicals in the showerhead, thereby avoiding the generation of particles. In order to maximize free radical life and free radical transmittance, Teflon coating can be performed. The remote plasma source can be, for example, a microwave plasma source.

The silicon precursor compound is preferably substantially free of halogen ions (such as chloride ions) or metal ions (such as aluminum, iron, nickel, and chromium). As used herein, the term "substantially free" when it refers to halogen ions (halides) such as chloride and fluoride, bromide, and iodide, and when it refers to metal ions such as Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Cr ³⁺ means less than 10 ppm (by weight), or less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and preferably 0 ppm (for example, greater than about 0 ppm to less than about 1 ppm). It is reported that chlorides or metal ions can be used as decomposition catalysts for silicon precursors. A significant amount of chloride in the final product can cause degradation of the silicon precursor. The gradual degradation of the silicon precursor may directly impact the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. In addition, the storage life or stability is negatively impacted by the higher degradation rate of the silicon precursor, making it difficult to guarantee a storage life of 1 to 2 years. Furthermore, it is reported that some silicon precursors will form combustible and/or pyrophoric gases such as hydrogen and silane after decomposition. Therefore, the formation of these combustible and/or spontaneous gaseous by-products causes safety and performance problems in the accelerated decomposition of the silicon precursor.

The composition according to the present invention that is substantially free of halide can be achieved by (1) reducing or eliminating the source of chloride during chemical synthesis, and/or (2) implementing an effective purification process to remove the crude product The chlorine removal compound makes the final purified product substantially free of chloride. The source of chloride may be reduced during the synthesis by using halogen-free reagents such as chlorodisilanes, bromodisilanes, or iododisilanes to avoid the generation of halide-containing by-products. In addition, the aforementioned reagents should be substantially free of chloride impurities so that the resulting crude product is substantially free of chloride impurities. In a similar way, the synthesis should not use halide-based solvents, catalysts, or solvents that contain unacceptably high concentrations of halide contaminants. The crude product can also be processed by different purification methods to make the final product substantially free of halides such as chlorides. This method has been clearly described in the prior art and can include, but is not limited to, purification processes such as distillation or adsorption. Distillation often uses the difference between boiling points to separate impurities from the desired product. Adsorption can also be used to take advantage of the differential adsorption properties of multiple components to promote separation so that the final product is substantially free of halide. Adsorbents such as, for example, commercially available MgO-Al ₂ O ₃ blends can be used to remove halides such as chlorides.

The method used to form the film or coating described herein is a flowable chemical deposition process. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, plasma enhanced chemical vapor deposition (PECVD), remote plasma chemical vapor deposition (RPCVD), hot filament chemical vapor deposition (HWCVD) ) Or plasma enhanced cyclic CVD (PECCVD) process. As used herein, the term "flowable chemical vapor deposition process" means exposing a substrate to one or more volatile precursors, which react and/or decompose on the surface of the substrate to provide flowable Of the oligomeric silicon-containing species and then rely on further processing to make any process for the solid film or material. Although the precursors, reagents and sources used herein may sometimes be described as "gaseous", it is understood that the precursors may be liquid or solid. The precursors are directly vaporized, bubbled, or sublimated, or use no inert gas. Ship to the reactor. In some cases, the vaporized precursor can pass through the plasma generator. In a specific example, the film is deposited using a plasma-based (for example, remote generation or on-site) CVD process. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber or a deposition chamber.

In some specific examples, the substrate may be exposed to one or more pre-deposition treatments such as, but not limited to, plasma treatment, heat treatment, chemical treatment, ultraviolet exposure, electron beam exposure, and combinations thereof to affect a portion of the film. Or more nature. These pre-deposition treatments can be carried out under an atmosphere selected from the group consisting of inert, oxidizing and/or reducing.

Energy is applied to at least one of the compound, nitrogen-containing source, oxygen source, other precursors, or a combination thereof to initiate a reaction and form the silicon-containing film or coating on the substrate. This energy can be achieved by, but not limited to, heat, plasma, pulsed plasma, spiral plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods and combinations thereof , To provide. In some embodiments, the secondary RF frequency source can be used to modify the plasma characteristics at the surface of the substrate. In the specific example where the deposition involves plasma, the plasma generation process may include a direct plasma generation process in which plasma is directly generated in the reactor, or plasma is generated outside the reactor and supplied to the reactor. Long-distance plasma generation process.

As previously mentioned, this method deposits a film on at least a portion of the surface of a substrate containing surface features. The substrate is placed in the reactor and the substrate is maintained at one or more temperatures ranging from about -20°C to about 100°C. In a specific embodiment, the temperature of the substrate is lower than the wall of the cabin. The substrate temperature is maintained at a temperature below 150 °C, preferably below 60 °C and most preferably below 40 °C and above -20 °C.

As previously mentioned, the substrate contains one or more surface features such as gaps. In a specific embodiment, the surface feature has a width of 100 µm or less, 1 µm or less, or 0.5 µm. In various specific examples, the aspect ratio (depth to width ratio) of the surface feature, if any, is 0.1:1 or greater, or 1:1 or greater, or 10:1 or greater, Or 20:1 or greater, or 40:1 or greater. The substrate can be single crystal silicon wafer, silicon carbide wafer, alumina (sapphire) wafer, glass plate, metal foil layer, organic polymer film, or it can be polymerized, glass, silicon or metallic 3- Dimensional objects. The substrate can include silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, gallium arsenide, gallium nitride and other films, including various materials well-known in the art. Come to coat. These coatings can completely coat the substrate, possibly with multiple layers of different materials, and can be partially etched to expose the underlying material layer. There may also be a photoresist material on the surface, and the photoresist material is exposed and developed with a pattern to partially coat the substrate.

In some embodiments, the reactor is at a pressure below atmospheric pressure or 50 Torr or less, or 10 Torr or less. In a preferred embodiment, the pressure of the reactor is maintained in the range of about 0.1 Torr to about 10 Torr. In another embodiment, the pressure of the reactor is maintained in the range of about 10 Torr to about 30 Torr to provide flowable silica with less shrinkage during thermal annealing.

In a general aspect, the present invention relates to methods and compositions as described in the above summary of the invention.

式I 其中R^1-4 係獨立地選自氫、直鏈或分支C₁ 至C₁₀ 烷基、直鏈或分支C₃ 至C₁₀ 烯基、直鏈或分支C₃ 至C₁₀ 炔基、C₁ 至C₆ 二烷基胺基及C₆ 至C₁₀ 芳基，n= 1、2、3、4。較佳為R^1-4 係獨立地選自氫及甲基； 提供活化氧來源至該反應器中以與該至少一化合物反應形成膜並且覆蓋該表面特徵的至少一部分，該氧來源係藉由，舉例來說，原位電漿(in-situ plasma)或遠距電漿活化； 於約100℃至1000℃的一或更多溫度下將該膜退火，並且視需要地接著此熱退火步驟之後，將該塗層暴露於UV輻射以供進一步退火；及 視需要地於約100℃至約1000℃的一或更多溫度下用氧源處理該基材，以將含矽膜形成於該表面特徵的至少一部分上。於某些具體實例中，該氧源係選自由水蒸氣、水電漿、臭氧、氧、氧電漿、氧/氦電漿、氧/氬電漿、氮氧化物電漿、二氧化碳電漿、過氧化氫、有機過氧化物及其混合物所組成的群組。於各個不同具體實例中，將該方法步驟重複進行到該表面特徵被該含矽膜填充。於水蒸氣用作氧源的具體實例中，該基材溫度介於約-20℃至約40℃或約-10℃至約25℃。In another aspect, a method for depositing a silicon-containing film is provided, the method comprising: placing a substrate containing surface features in a reactor, the substrate being maintained at a temperature between about -20°C and about One or more temperatures of 150°C and the pressure of the reactor is maintained at 100 Torr or lower; at least one compound is introduced, and the compound is selected from the group consisting of at least one compound having the structure shown below group:

Formula I wherein R ^1-4 are independently selected from hydrogen, linear or branched C ₁ to C ₁₀ alkyl, linear or branched C ₃ to C ₁₀ alkenyl, linear or branched C ₃ to C ₁₀ alkynyl, C ₁ to C ₆ dialkylamino group and C ₆ to C ₁₀ aryl group, n=1, 2, 3, 4. Preferably, R ^1-4 are independently selected from hydrogen and methyl; an activated oxygen source is provided to the reactor to react with the at least one compound to form a film and cover at least a part of the surface features, the oxygen source is obtained by For example, in-situ plasma or remote plasma activation; annealing the film at one or more temperatures of about 100°C to 1000°C, and optionally following this thermal annealing step Afterwards, the coating is exposed to UV radiation for further annealing; and if necessary, the substrate is treated with an oxygen source at one or more temperatures ranging from about 100°C to about 1000°C to form a silicon-containing film on the At least part of the surface features. In some specific examples, the oxygen source is selected from water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen/helium plasma, oxygen/argon plasma, nitrogen oxide plasma, carbon dioxide plasma, over The group consisting of hydrogen oxide, organic peroxides and their mixtures. In various specific examples, the method steps are repeated until the surface features are filled with the silicon-containing film. In a specific example in which water vapor is used as the oxygen source, the temperature of the substrate is about -20°C to about 40°C or about -10°C to about 25°C.

式I 其中R^1-4 係獨立地選自氫、直鏈或分支C₁ 至C₁₀ 烷基、直鏈或分支C₃ 至C₁₀ 烯基、直鏈或分支C₃ 至C₁₀ 炔基、C₁ 至C₆ 二烷基胺基及C₆ 至C₁₀ 芳基，n= 1、2、3、4。較佳為R^1-4 係獨立地選自氫及甲基； 提供電漿來源，遠距或原位，至該反應器中以與該化合物反應形成塗層於該表面特徵的至少一部分上。於一特定具體實例中，與該化合物反應形成塗層的電漿來源係選自由以下所組成的群組：氮電漿；包含氮和氦的電漿；包含氮和氬的電漿；氨電漿；包含氨和氦的電漿；包含氨和氬的電漿；氦電漿；氬電漿；氫電漿；包括氫和氦的電漿；包含氫和氬的電漿；包含氨和氫的電漿；有機胺電漿；及其混合物；及 於介於約100℃至1000℃或約100℃至400℃的一或更多溫度下將該塗層退火以將含矽膜形成於該表面特徵的至少一部分上。此熱退火步驟之後可視需要地使該塗層暴露於UV輻射以供進一步退火。對於可流動的電漿強化CVD方法，可重複上述步驟直到該表面特徵被填充緻密化膜為止。In another aspect, a method for depositing a silicon-containing film is provided. The silicon-containing film is selected from silicon nitride, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride film. The method comprises: placing a substrate containing surface features in a reactor, which is heated to a temperature between -20°C and about 150°C and maintained at 100 Torr or less The pressure of at least one compound is introduced into the reactor, and the compound is selected from the group consisting of at least one compound having the structure shown below:

Formula I wherein R ^1-4 are independently selected from hydrogen, linear or branched C ₁ to C ₁₀ alkyl, linear or branched C ₃ to C ₁₀ alkenyl, linear or branched C ₃ to C ₁₀ alkynyl, C ₁ to C ₆ dialkylamino group and C ₆ to C ₁₀ aryl group, n=1, 2, 3, 4. Preferably, R ^1-4 are independently selected from hydrogen and methyl; provide a source of plasma, remotely or in situ, into the reactor to react with the compound to form a coating on at least a part of the surface feature. In a specific embodiment, the source of plasma that reacts with the compound to form a coating is selected from the group consisting of: nitrogen plasma; plasma containing nitrogen and helium; plasma containing nitrogen and argon; ammonia electricity Plasma; Plasma containing ammonia and helium; Plasma containing ammonia and argon; Helium plasma; Argon plasma; Hydrogen plasma; Plasma containing hydrogen and helium; Plasma containing hydrogen and argon; Plasma containing ammonia and hydrogen And mixtures thereof; and annealing the coating at one or more temperatures ranging from about 100°C to 1000°C or about 100°C to 400°C to form a silicon-containing film on the At least part of the surface features. After this thermal annealing step, optionally expose the coating to UV radiation for further annealing. For the flowable plasma enhanced CVD method, the above steps can be repeated until the surface feature is filled with the densified film.

The precursors of the present invention and other related formulations containing one or more components contained therein can be stored, transported and transported in glass, plastic or metal containers or other suitable containers known in the art, for example, the following US Patent No. 4,828,131 No. 6,077,356; No. 6,526,824; No. 7,124,913; and No. 7,261,118 disclosed containers, all of these documents are hereby incorporated by reference in their entirety.

Metal containers with plastic or glass substrates can also be used. Preferably, the material is stored and transported in a hermetically sealed high-purity stainless steel or nickel alloy container with an inert gas in the headspace. Optimally, the material is stored and transported in a hermetically sealed high-purity stainless steel or nickel alloy container equipped with a down tube and an outlet communicating with the vapor space of the container; allowing the product to be liquid It is transported from the down tube or steam from the outlet connection connected with the steam. In the latter case, the down tube may optionally be used to introduce carrier gas into the container to promote the evaporation of the mixture. In this specific example, the down tube and vapor outlet connection are equipped with a highly complete packless valve. Although it is preferable to transport liquids to avoid separation of the components of the formulations described herein, it should be noted that the formulations of the present invention match the vapor pressures of the components close enough to enable the formulation to be transported as a vapor mixture. The stainless steel may preferably be selected from UNS alloy numbers S31600, S31603, S30400, S30403, S31700, S31703, S31500, S31803, S32750 and S31254. The nickel alloy can preferably be selected from UNS alloy numbers N06625, N10665, N06022, N10276 and N06007. Preferably, the container is made of alloy S31603 or N06022, whether uncoated, internally electropolished, or internally coated with fluoropolymer.

The formulations described herein can be used to provide rapid and uniform deposition of flowable silicon oxide films. The formulations described herein can be used with another reactant containing water and optionally co-solvents, surfactants, and other additives and deposited on a substrate. The distribution or delivery of the reaction formula can be achieved by direct liquid injection, spraying, dipping, co-condensation or centrifugal spin coating. The formulation is then allowed to react until a solid film or body is obtained. Then, inert gas, vacuum, heat, or external energy sources (light, heat, plasma, electron beam, etc.) can be used to remove unreacted volatile substances, including solvents and unreacted water, to promote the condensation of the film. The formulation of the present invention can preferably be transported to the substrate contained in the deposition chamber in the form of a process fluid such as, but not limited to, gas phase, droplets, mist, dense mist, aerosol, sublimation solid or a combination with water. , And optionally co-solvents and other additives are added as process fluids such as gas, vapor, aerosol, mist or a combination thereof. Preferably, the formulation of the present invention condenses or dissolves on the surface of the substrate to form a condensation film, which can be advantageously maintained at a temperature lower than the temperature of the bulkhead. The blended deposition precursor and catalyst of the present invention can react on the surface of the substrate at a uniform rate, so that the reaction product becomes a non-volatile film. Then the unreacted precursors, water, co-solvents and additives can be removed by gas purging, vacuum, heating, external radiation (light, plasma, electron beam, etc.) until a stable solid silicon-containing film is obtained until.

Throughout the specification, when used herein, the term "silicon oxide" means a film containing silicon and oxygen, and the film is selected from stoichiometric or non-stoichiometric silicon oxide, carbon-doped silicon oxide, silicon carbon oxynitride and The group consisting of its mixture. Examples of silicon-containing films or silicon nitride films formed using silicon precursors and processes of formula I or II have this formula Si _x O _y C _z N _v H _w , where Si is between about 10% and about 50% ; O is between about 0% to about 70%; C is between about 0% to about 40%; N is between about 10% to about 75% or about 10% to 60%; and H is between about 0% to about 10% atomic weight%, where, for example, when measured by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS), x+y+z+v+w=100 atomic weight%.

Throughout the specification, the term "feature" when used herein means a semiconductor substrate or a semi-finished semiconductor substrate having through holes, trenches, and the like.

The following examples illustrate some specific examples of the invention. These embodiments do not limit the scope of the attached patent application. Example

The flowable chemical vapor deposition (FCVD) film is deposited on a medium resistivity (8-12 Ωcm) single crystal silicon wafer substrate and Si patterned wafer. Regarding the patterned wafer, the preferred pattern width is 20 to 100 nm, and the aspect ratio is 5:1 to 20:1. The deposition is performed by the modified FCVD chamber of the Applied Materials Precision 5000 system, using dual plenum showerheads. The cabin has direct liquid injection (DLI) transport capabilities. The precursor is kept in a liquid state by the transport temperature according to the boiling point of the precursor. In order to deposit an initially flowable nitride film, the typical liquid precursor flow rate is between about 100 to about 5000 mg/min, preferably 1000 to 2000 mg/min; the tank pressure is between about 0.75 to 12 Torr, preferably 0.5 to 2 Torr. In particular, the long-distance power is supplied by a MKS microwave generator operating from 2 to 8 Torr with a frequency of 2.455 GHz from 0 to 3000 W. In order to make the film as deposited flowable densified using the modified film based PECVD chamber at 100 to 1000 ^o C, preferably at 300 to 400 ^o C, in a vacuum thermal annealing, and / or UV curing. Measure the thickness and refractive index (RI) at 632 nm by SCI reflectometer or Woollam ellipsometer. The typical film thickness is between about 10 to about 2000 nm. The bonding property hydrogen content (Si-H, CH, and NH) of the silicon-based film is measured and analyzed by Nicolet transmission Fourier transform infrared spectroscopy (FTIR) equipment. X-ray photoelectron spectroscopy (XPS) analysis was performed to determine the elemental composition of the film. A mercury probe is used to measure electrical properties including dielectric constant, leakage current, and breakdown electric field. The fluidity and gap filling effect on the aluminum patterned wafer were observed by a cross-sectional scanning electron microscope (SEM) using a Hitachi S-4800 system at a resolution of 2.0 nm.

2,2,5,5-Tetramethyl-2,5-disila-1-oxolane (TMDSOCH) is a flowable SiOC film deposition for remote plasma sources (RPS). The TMDSOCH flow rate is 2100 mg/min, the oxygen flow rate is 3000 sccm, and the pressure is 2.5 Torr. The substrate temperature is 40°C. The microwave power is 2000 W. The as-deposited film was thermally annealed at 300°C for 5 minutes, and then UV cured at 400°C for 4 minutes. The thickness and refractive index of the as-deposited film were 1675.8 nm and 1.431. After thermal annealing, the thickness and refractive index were 1249.9 nm and 1.423, indicating that some volatile oligomers were lost at elevated temperature. The elemental composition of the thermally annealed film measured by XPS is 30.6% C, 40.0% O, and 29.4% Si. The dielectric constant of the film after thermal annealing was 3.50, which was attributed to some hygroscopicity caused by dangling bonds. After UV curing, the thickness and refractive index were 968.3 nm and 1.349, indicating that the film was modified by UV curing and introduced some porosity. The elemental composition of the film after thermal annealing and UV curing measured by XPS was 21.6% C, 45.4% O and 33.0% Si, indicating that there was carbon loss in the film cured by UV. The dielectric constant of the UV cured film was 2.56. The cross-sectional SEM indicates that a good gap filling has been achieved on the patterned wafer. Figure 1 and Figure 2 show good gap filling. The film is thermally annealed and UV cured. Figure 3 shows the FTIR spectra of (a) the as-deposited film, (b) the film after thermal annealing, and (c) the film after thermal annealing and UV curing.

Although the principle of the present invention has been described above with preferred specific examples, it should be clearly understood that this description is only performed by way of example, and is not intended to limit the scope of the present invention.

Figure 1 is an SEM photograph of a patterned wafer with an organosilicate glass film deposited according to Example 1 after thermal annealing;

Figure 2 is an SEM photograph of the patterned wafer depicted in Figure 1 after the UV curing step;

3 is an FTIR diagram of the original deposited film according to Example 1 before thermal annealing or UV curing;

4 is the FTIR image of the as-deposited film according to Example 1 after thermal annealing but before UV curing; and

5 is an FTIR image of the as-deposited film according to Example 1 after thermal annealing and after UV curing.

Claims (9)

A flowable chemical vapor deposition method for forming a silicon-containing film on a substrate, the method comprising placing the substrate in a reaction chamber and placing at least one cyclic siloxane compound represented by formula I and At least one activated species was introduced into the cabin,

Wherein R ^1-4 is independently selected from hydrogen, linear or branched C ₁ to C ₁₀ alkyl, linear or branched C ₃ to C ₁₀ alkenyl, linear or branched C ₃ to C ₁₀ alkynyl, di- C ₁ to C ₆ -alkylamino group and C ₆ to C ₁₀ aryl group, and n=1, 2, 3, 4, wherein the reactor conditions are controlled so that the silicon-containing compound and the activated species react and react with each other The substrate is condensed into a flowable film, and the at least one activated species is activated remotely from the reaction chamber. Such as the method of claim 1, wherein the substrate includes surface features with a high aspect ratio gap therebetween, and wherein the silicon-containing compound reacts with the activated species to form the flowable film in the gap. Such as the method of the second item in the scope of patent application, wherein the high aspect ratio gap has an aspect ratio ranging from 3:1 to 10:1. Such as the method of the first item in the scope of the patent application, wherein the activated species is produced using a remote plasma source, a remote microwave source, or a remote hot-wire system. Such as the method of claim 1, wherein the at least one activated species is selected from water vapor, ozone, oxygen, oxygen/helium, oxygen/argon, and nitrogen oxidation by plasma source or remote microwave source Oxidants produced by species in the group consisting of carbon dioxide, hydrogen peroxide, organic peroxides and their mixtures. Such as the method of claim 1, wherein the at least one cyclic siloxane compound comprises 2,2,5,5-tetramethyl-1-oxa-2,5-disilolane and 2 , One or both of 2,6,6-tetramethyl-1-oxa-2,6-disilane. Such as the method of the first item of the patent application, which additionally includes: processing the flowable film by a processing method selected from the group consisting of plasma, UV radiation and thermal annealing. Such as the method of item 7 of the scope of patent application, wherein the step of processing the flowable film by the processing method converts the flowable film into a dielectric material. Such as the method of claim 1, wherein the at least one activated species acts on a mixture of nitrogen, nitrogen and helium, a mixture of nitrogen and argon, ammonia, ammonia, and helium by a plasma source or a remote microwave source A mixture of ammonia and argon, a mixture of helium, argon, hydrogen, a mixture of hydrogen and helium, a mixture of hydrogen and argon, a mixture of ammonia and hydrogen, organic amines and their mixtures are produced by species in the group.

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